Hannah Noriza Abot BS ChE-1 CHEA 1201 (MW 4:30-6:30) March 9, 2020
PRECIPITATION TITRATION
- It is a titrimetric method which involves the formation of precipitates during the
experiment of titration. The titrant reacts with the analyte and forms an insoluble
substance.
- The main principle of precipitation titration is that the quantity of the precipitating
reagent or precipitant is equal to substance being precipitated.
- Precipitation titrations are fast and the stoichiometry is reproducible. They are also
complete and can be quantified depending on the solubility product. Additionally, an
indicator can be used to find the equivalence point or end point.
METHODS OF PRECIPITATION TITRATION
Volhard’s Method– it involves the titration of bromides, iodides, and chlorides in an acidic
medium. This is an indirect method for chloride determination where an excess amount of
standard Ag+ is added to the chloride solution containing Fe 3+ as an indicator. The excess Ag + is
then titrated with standard SCN- (thiocyanate) until a red color is obtained.
Fe3+ + SCN- Fe(SCN)2-
Indicator system is very sensitive and usually good results are obtained. However, the acidic
medium and SCN- titrant increases the solubility of precipitate leading to significant errors.
Fajan’s Method –this method uses the reaction between the precipitate formed and the
indicator. The indicator used is DCF (dichlorofluoroscein). Fluoroscein and its derivatives are
adsorbed to the surface of colloidal AgCl. After all chloride is used, the first drop of Ag + will
react with fluorescein (FI-) forming a reddish color.
Ag+ + FI- AgF
It makes use of adsorption indicator which makes the titration rapid and accurate. However,
this method is pH dependent as the indicator must be in the ionized form.
Mohr’s Method –this method utilizes chromate as an indicator. Chromate forms a precipitate
with Ag+ but this precipitate has a greater solubility than that of AgCl. Therefore AgCl is formed
first and after all Cl- is consumed, the first drop of Ag+ in excess will react with the chromate
indicator giving a reddish precipitate.
2Ag+ + CrO42- Ag2CrO4
This method is simple, direct, accurate, and uses potassium chromate as indicator which is
accessible and affordable. However, it is only suitable for titration of chloride, bromide, and
cyanide. Errors can be introduced due to the need of excess titrant before endpoint color is
visible. Moreover, this method requires an acidic medium, hence it cannot take place in basic or
neutral solutions.
Sample Problems:
Hannah Noriza Abot BS ChE-1 CHEA 1201 (MW 4:30-6:30) March 9, 2020
1. A mixture containing only KCl and NaBr is analyzed by Mohr method. A 0.3172-g sample
is dissolved in 50-mL of water and titrated to the Ag 2CrO4 end point, requiring 36.85-mL
of 0.1120 M AgNO3. A blank titration requires 0.71 mL of titrant to reach the same end
point. Report the % w/w (weight concentration) KCl in the sample.
Solution:
VAg= 36.85 mL – 0.71 mL = 36.14 mL x (1L/1000 mL) = 0.03614 L AgNO3
(0.1120 M AgNO3) x (0.03614 L AgNO3) = 4.048 x 10-3 mol AgNO3
moles KCl + moles NaBr = 4.048 x 10-3
g KCl g NaBr
moles KCl= moles NaBr=
74.551 g KCl/molKCl 102.89 g NaBr /mol NaBr
g KCl g NaBr
+ = 4.048 x 10-3
74.551 g KCl/molKCl 102.89 g NaBr /molNaBr
g NaBr = 0.3172 g – g KCl
g KCl 0.3172 g−gKCl
+ = 4.048 x 10-3
74.551 g KCl/molKCl 102.89 g NaBr /molNaBr
1.341 x 10-2 (g KCl) + 3.083 x 10-3 – 9.719 x 10-3 (g KCl) = 4.048 x 10-3
3.69 x 10-3 (g KCl) = 9.65 x 10-4
g KCl = 0.262
(0.262 g KCl / 0.3172 g sample) x 100 = 82.6% w/w KCl
2. A 0.32 g sample containing KCl (mw= 74.551) is dissolved in 50 mL of water and titrated
to the Ag2CrO4 end point, requiring 16.9 mL of 0.1 M AgNO 3. A blank titration requires
0.7 mL titrant to reach the same end point. Report the % w/w KCl in the sample.
Solution:
VAg= 16.9 mL – 0.7 mL = 16.2 mL x (1L/1000 mL) = 0.0162 L AgNO3
(0.1 M AgNO3) x (0.0162 L AgNO3) = 1.62 x 10-3 moles of Ag+ = moles of KCl
g KCl = (1.62 x 10-3) x (74.551) = 0.12 g
% KCl = [(0.12)/ (0.32)] x 100 = 37.5%
Hannah Noriza Abot BS ChE-1 CHEA 1201 (MW 4:30-6:30) March 9, 2020
REFERENCES
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Harvey David - Modern Analytic Chemistry - Стр 38. (n.d.). Retrieved March 8, 2020, from
https://studfile.net/preview/409180/page:38/
Libretexts. (2019, June 5). 9.5: Precipitation Titrations. Retrieved March 8, 2020, from
https://chem.libretexts.org/Courses/Northeastern_University/09:_Titrimetric_Methods/9.5:_Preci
pitation_Titrations
Precipitation Titration. (n.d.). Retrieved March 8, 2020, from
https://fac.ksu.edu.sa/sites/default/files/unit_13_-precipitation_titration_-_subjects_0.pdf
Precipitation Titration Definition, Example, Types, Indicators On BYJU'S. (2019, March 4).
Retrieved March 4, 2020, from https://byjus.com/chemistry/precipitation-titration/
Rahman, A. (2014, October 15). Precipitation Titration. Retrieved March 8, 2020, from
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